The invention relates generally to a rapid, direct process for producing pure organosilicon compositions by hydrosilation of olefins and oxirane-containing olefins with silicon hydride groups by using extremely low levels of a platinum catalyst. Generally, hydrosilation catalysts are complexes of platinum, palladium, rhodium, iridium, iron or cobalt. Many of these transition metal hydrosilation catalysts also promote ring-opening polymerization of oxiranes in the presence of silicon hydrides. In this invention the hydrosilation reaction proceeds such that any oxirane rings in both the olefin and organosilicon product remain intact. Furthermore, the invention also relates to curable oxirane-containing siloxane (epoxysiloxane) compositions made by the above method. The ring-opening polymerization reaction during production of an oxirane-containing organosilicon composition may be undesirable as the oxirane polymerization may cause the reaction mixture to gel partially or completely, resulting in the loss of the entire batch and in loss of considerable time in cleanup of the insoluble gelled resin. Partial gelation due to the ring-opening polymerization reaction can occur during hydrosilations such that reproducible batch-to-batch viscosity of the oxirane-containing organosilicon product is difficult to obtain. Such reproducibility in viscosity is highly preferred in commercial applications of oxirane-containing organosilicon compositions and these materials may be used in applications such as coatings, and encapsulents and lens material for high luminosity light emitting diodes.
In some instances product oxirane-containing organosilicon compositions have been found to slowly gel on storage at room temperature in the presence of precious metal hydrosilation catalysts due to the oxirane ring-opening polymerization reaction, thus shortening the product shelf life. While this storage problem can be partially alleviated by deactivating the transition-metal-complex catalyst with an inhibitor, such as dodecyl mercaptan or 2-mercaptobenzothiazole in the case of platinum complexes, it would be preferable to not incorporate this extra component and additional process step into the process of producing the oxirane-containing organosilicon compositions. This storage problem can also be alleviated by ensuring complete consumption of the silicon hydride during the preparative process.
In general, careful control of batch temperature and oxirane-containing olefin feed rate during the synthesis, followed by the above-mentioned inactivation of the catalyst after the completion of the hydrosilation reaction is required in order to minimize the oxirane ring-opening polymerization reaction.
Certain hydrosilation catalysts containing phosphine ligands are known. For example, RhCl(PPh3)3 (Wilkinson""s catalyst) efficiently catalyzes the hydrosilation reaction between SiH-containing silanes and siloxanes and vinyl oxiranes. Other rhodium-based catalysts have been reported to selectively promote the hydrosilation reaction without the promotion of an oxirane ring-opening polymerization reaction. A variety of epoxy-functionalized silicone monomers and oligomers have been synthesized using these catalysts. However, most of the catalysts traditionally used in the hydrosilation reaction of oxirane-containing olefins, particularly Pt-containing catalysts, promoted the oxirane ring-opening polymerization reaction, and therefore did not permit the selective preparation of oxirane-containing organosilicon compositions by the hydrosilation route.
It is therefore desirable to provide an efficient method for hydrosilation to prepare organosilicon compositions in the presence of a catalyst in amounts which do not promote the oxirane ring-opening polymerization of either the olefin or the organosilicon product. Such a method will provide a means for preparing an oxirane-containing organosilicon composition having a reproducible viscosity and longer shelf life.
The present invention relates to a method for preparing an organosilicon composition, said method comprising:
preparing a mixture comprising:
at least one olefin;
at least one silicon compound comprising silicon hydride groups, said olefin and said silicon compound being present in amounts such that the mixture comprises at least one reactive double bond per Sixe2x80x94H group;
a hydrosilation catalyst comprising at least one platinum (II) complex having the formula:
PtL2X2,
wherein each L is independently selected from the group consisting of ER3, E(OR)3, and E(NR2)3; each E is independently selected from the group consisting of phosphorus, arsenic, and antimony; each R is independently a hydrocarbyl group; and each X is independently selected from the group consisting of chloride, bromide, and iodide; said hydrosilation catalyst being present in an amount corresponding to an amount of platinum, said amount of hydrosilation catalyst being such that the amount of platinum present in said mixture is in a range between about 1 part per billion to less than 1000 parts per billion relative to a total weight of a product organosilicon composition;
optionally at least one solvent; and
reacting the mixture in the presence of oxygen at a temperature in a range from about ambient temperature to about 300xc2x0 C., to produce said product organosilicon composition.
In one aspect of the present invention, the amount of hydrosilation catalyst used is such that the amount of platinum present is equivalent to more than about 1 part per billion (ppb) platinum and less than 1000 ppb platinum, the amount of platinum in parts per billion being relative to the total weight of the product organosilicon composition.
In a further aspect, the present invention relates to organosilicon compositions prepared by the method of the invention. In one aspect the present invention relates to stable oxirane-containing organosilicon compositions prepared by the method of the present invention.
As used herein, elements of Groups of the Periodic Table are made in reference to the xe2x80x9cPeriodic Table of the Elementsxe2x80x9d, as published in xe2x80x9cChemical and Engineering Newsxe2x80x9d, 63(5), 27, 1985, said Table being incorporated herein by reference. In this format, the Groups are numbered 1 to 18.
The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included herein. In this specification and in the claims that follow, reference will be made to a number of terms, which are defined to have the following meanings.
The singular forms xe2x80x9caxe2x80x9d, xe2x80x9canxe2x80x9d and xe2x80x9cthexe2x80x9d include plural referents unless the context clearly dictates otherwise.
As used herein, the term xe2x80x9colefinxe2x80x9d refers to a compound incorporating a carbon-carbon double bond.
As used herein the term xe2x80x9cepoxyolefinxe2x80x9d refers to an olefin, which also comprises an oxirane ring. Thus, 4-vinyl cyclohexene oxide is both an olefin and an epoxyolefin.
As used herein the term xe2x80x9csilicon compound comprising silicon hydride groupsxe2x80x9d refers to a silicon compound comprising at least one SiH group. An example of a xe2x80x9csilicon compound comprising hydride groupsxe2x80x9d is trimethylsilane (Me3SiH). Triphenylsilane is also an example of a xe2x80x9csilicon compound comprising SiH groupsxe2x80x9d as is tetramethydisilane ((HSiMe2)2).
The term xe2x80x9csilicon hydridexe2x80x9d when used to describe a complete chemical compound has the same meaning as the term xe2x80x9csilicon compound comprising silicon hydride groupsxe2x80x9d. The term xe2x80x9csilicon hydride groupxe2x80x9d refers to the SiH moiety present in a xe2x80x9csilicon compound comprising silicon hydride groupsxe2x80x9d. For example, trimethylsilane (Me3SiH) is a xe2x80x9csilicon hydridexe2x80x9d which contains a xe2x80x9csilicon hydride groupxe2x80x9d, meaning that it contains an SiH moiety.
As used herein, the term xe2x80x9cproduct organosilicon compositionxe2x80x9d refers to the product formed in a hydrosilation reaction between at least one xe2x80x9csilicon compound comprising silicon hydride groupsxe2x80x9d as defined herein, and at least one xe2x80x9colefinxe2x80x9d as defined herein.
The term xe2x80x9chydrocarbyl groupxe2x80x9d, as used herein, denotes a monovalent, linear, branched, cyclic, or polycyclic group, which contains carbon and hydrogen atoms. The hydrocarbyl group may optionally contain atoms in addition to carbon and hydrogen selected from Groups 15, and 16 of the Periodic Table. Examples of monovalent hydrocarbyl groups include the following: C1-C30 alkyl; C1-C30 alkyl substituted with one or more groups selected from C1-C30 alkyl, C3-C15 cycloalkyl or aryl; C3-C15 cycloalkyl; C3-C15 cycloalkyl substituted with one or more groups selected from C1-C20 alkyl, C3-C15 cycloalkyl or aryl; C6-C15 aryl; and C6-C15 aryl substituted with one or more groups selected from C1-C30 alkyl, C3-C15 cycloalkyl or aryl group; where aryl preferably denotes a substituted or unsubstituted phenyl, naphthyl, or anthracenyl group.
The present invention is based upon the unexpected discovery that less than parts per million (ppm) levels of platinum, in the form of platinum(II) complexes comprising organophosphorus, organoarsenic, or organoantimony ligands, effectively catalyze the hydrosilation of an olefin with a silicon hydride to prepare an organosilicon composition. The use of such low levels of platinum catalyst in hydrosilation chemistry is unprecedented. For example, the prior art teaches that catalyst levels in excess of 1 part per million (ppm) of should be employed. The problem with known preparations of oxirane-containing organosilicon compositions is that the hydrosilation catalysts employed also catalyze the undesired polymerization of oxirane groups in either the oxirane-containing olefin starting material, the oxirane-containing organosilicon product, or both, which may lead to gel formation. Addition of, for example, high boiling amines inhibits gel formation, but also inhibits the hydrosilation reaction itself, thereby leading to incomplete conversion of reactants to products. To overcome the inhibitory effect of the stabilizer, higher loadings of the platinum(II) catalyst is required, which greatly increases the process cost, increases the reaction time, and discolors the product.
As stated previously, the method of the present invention provides an efficient and highly selective method for preparing an organosilicon composition under conditions which promote hydrosilation of an olefin with a silicon hydride to produce an organosilicon composition. Where the olefinic compound comprises an oxirane, under the conditions of the present invention, the oxirane rings of the starting material and the product oxirane-containing organosilicon composition remain substantially intact. By xe2x80x9csubstantially intactxe2x80x9d it is meant that the level of oxirane ring opening, if any, does not produce a measurable effect on the viscosity of the product oxirane-containing organosilicon composition. Typically, this means that greater than 95 percent, more preferably more than 98 percent, and even more preferably more than 99 percent of the oxirane rings present in the starting material and product remain intact during the hydrosilation reaction.
The silicon hydride can be any type of a silicon compound having at least one Sixe2x80x94H group. There is no restriction on the range of functionality that can be present in the silicon hydride, so long as the functionality is inert under the hydrosilation reaction conditions. Examples of such inert functionality include hydrocarbyl, alkoxy, and aryloxy groups. Examples of silicon hydrides include tetramethyldisiloxane, triethoxysilane, methyldimethoxysilane, triethylsilane, methyldiethoxysilane, and the like. The silicon hydride can be a silane, a siloxane, or mixtures thereof. For the purposes of describing the present invention, a silane is defined as a compound having at least one hydride group and no Sixe2x80x94Oxe2x80x94Si linkage, and a siloxane is defined as a compound having at least one hydride group and at least one Sixe2x80x94Oxe2x80x94Si linkage. Both linear and branched structural variations of the silicon hydrides are included within the scope of the present invention . Besides linear and branched structures, the siloxanes may also comprise cyclic structures. Suitable examples of cyclic siloxanes having at least one hydride group include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and the like. Examples of linear organohydrogensiloxanes include 1,1,3,3-tetramethyldisiloxane, bis(dimethylsilyl)silicate, poly(dimethylsiloxane)-poly(methylhydrogensiloxane) copolymer, dialkylhydrogensilyloxy-endstopped polydialkylsiloxane, copolymer containing at least three alkylhydrogensilyloxy groups, (e.g., (CH3)2(H)SiO[(CH3)2SiO]x[(CH3)(H)SiO]ySi(H)(CH3)2, where xe2x80x9cxxe2x80x9d and xe2x80x9cyxe2x80x9d are greater than or equal to 1), and the like. A mixture comprising cyclic and linear silicon hydrides may also be used as the hydrosilation reagent, thus leading to a rich diversity of hydrosilylated products.
The hydrosilation catalyst is a platinum(I) complex having the formula, PtL2X2,wherein each L is independently selected from the group consisting of ER3, E(OR)3, and E(NR2)3; each E is independently selected from the group consisting of phosphorus, arsenic, and antimony; each R is independently a hydrocarbyl group; and each X is independently selected from the group consisting of chloride, bromide, and iodide. Suitable examples of xe2x80x9cLxe2x80x9d include, but are not limited to, trimethylphosphine, triethylphosphine, tritolylphosphine, triphenylphosphine, triphenylstibine, triphenylarsine, tri-n-butylphosphine, tri-n-butylstibine, tri-n-butylarsine, trimethylphosphine, diphenylmethylphosphine, dimethylphosphine, trimethylphosphite, triethylphosphite, tri-n-butylphosphite, triphenylphosphite, tritolylphosphite, and the like.
Suitable examples of platinum(II) complexes include, but are not limited to, dichlorobis(triphenylphosphine)platinum, dibromobis(triphenylphosphine)platinum, diiodobis(triphenylphosphine)platinum, dichlorobis(triphenylstibine)platinum, dibromobis(triphenylstibine)platinum, diiodobis(triphenylstibine)platinum, dichlorobis(triphenylarsine)platinum, dibromobis(triphenylarsine)platinum, diiodobis(triphenylarsine)platinum dichlorobis(tri-n-butylphosphine)platinum, dibromobis(tri-n-butylphosphine)platinum, dichlorobis(trimethylphosphine)platinum, dichlorobis(triethylphosphine)platinum, dichlorobis(tritolylphosphine)platinum and the like. Catalyst compositions resulting from various combinations of xe2x80x9cLxe2x80x9d and xe2x80x9cXxe2x80x9d, as will be apparent to those skilled in the art, will also function satisfactorily in the hydrosilation reaction according to the method of the present invention.
The hydrosilation catalyst described above can be introduced into the hydrosilation reaction mixture either as a pre-formed complex, or prepared in situ. In one embodiment of the preparation of the hydrosilation catalyst in situ, a platinum compound, PtX2, wherein each xe2x80x9cXxe2x80x9d is independently selected from the group consisting of chloride, bromide, or iodide; is combined in the presence of the olefin and optionally the silicon compound containing Sixe2x80x94H groups, with a compound xe2x80x9cLxe2x80x9d having the formula, ER3, E(OR)3, or E(NR2)3, wherein E is selected from the group consisting of phosphorus, arsenic, and antimony; and each R is independently a hydrocarbyl group.
It has been unexpectedly discovered that ppb levels of the catalyst affords clean hydrosilation reaction products. The hydrosilation catalyst is present in an amount corresponding to an amount of platinum, said amount of hydrosilation catalyst being such that the amount of platinum present in said mixture is in a range between about 1 part per billion to less than 1000 parts per billion relative to the weight of the bydrosilation product. In a preferred embodiment, the amount of platinum present, as defined above, is from about 10 ppb to about 500 ppb relative to the weight of the hydrosilation product. In further preferred embodiment, the amount of platinum present, as defined above, is from about 50 ppb to about 200 ppb relative to the weight of the hydrosilation product.
The hydrosilation reaction can be carried out over a wide range of temperature. Although the invention is not limited by any theory of operation, it is believed that the temperature plays a crucial role in the activation of the platinum(II) complex catalyst through a process involving dissociation of the ligand L coordinated to the platinum center, thereby creating a coordinatively unsaturated site to interact with the olefin or the oxirane-containing olefin. The strength of the Pt(II)xe2x80x94L coordination bond in turn depends not only on the nature of E, but also on the nature of the xe2x80x9cRxe2x80x9d, xe2x80x9cORxe2x80x9d, or xe2x80x9cNR2xe2x80x9d-groups bonded to xe2x80x9cExe2x80x9d. The hydrosilation reaction can be carried out at any temperature from about ambient temperature to about 300xc2x0 C. In a preferred embodiment, the reaction can be carried out from about ambient temperature to about 200xc2x0 C.; while in a further preferred embodiment, the reaction can be carried out from about 50xc2x0 C. to about 150xc2x0 C.
A solvent may optionally be employed in the hydrosilation reaction. The use of a solvent is helpful when the silicon compound, the olefin, or both are solids or very viscous liquids, or when the reaction mixture thickens with time, whereby efficient stirring of the reaction mixture would be problematic. The use of a solvent may also aid in controlling the temperature of the reaction mixture. Suitable solvents that may be used according to the method of the present invention typically are those solvents having a boiling point from about 30xc2x0 C. to about 250xc2x0 C. In a preferred embodiment, the solvent has a boiling point from about 100xc2x0 C. to about 200xc2x0 C., and in a further preferred embodiment, the solvent has a boiling point from about 100xc2x0 C. to about 160xc2x0 C.
Suitable solvents for the hydrosilation reaction include those selected from the group consisting of C5-C30 substituted and unsubstituted aryl, aralkyl, and alkaryl hydrocarbons; linear and branched paraffins; and mixtures comprising any combination of the foregoing solvents. Examples of aromatic solvents include benzene, toluene, the individual xylene (ortho, meta, or para), and mixed isomeric xylenes, mesitylene, ethylbenzene, isopropylbenzene, (n-butyl)benzene, and the like. Examples of substituted aromatic solvents include those having alkoxy groups, such as anisole, alkylated anisoles, etc. Examples of linear and branched paraffin solvents include pentane, hexane, heptane, octane, isooctane, and other higher boiling commercially available paraffin mixtures. In particular embodiments, the solvent for the hydrosilation reaction is selected from the group consisting of toluene, the individual xylene (ortho, meta, or para), mixed isometric xylenes, or mixtures comprising any combination of the foregoing solvents. In another particular embodiment, the solvent can be the silicon hydride groups.
The presence of oxygen is desirable for carrying out the hydrosilation reaction. In one embodiment, the reaction can be carried out under an ambient atmosphere. By ambient atmosphere it is meant that the reaction mixture is exposed to the atmosphere during the hydrosilation reaction.
The olefin component of the hydrosilation reaction can, in general, be any ethylenically unsaturated compound. Ethylenically unsaturated compounds are defined herein as compounds that possess at least one carbon-carbon double bond. The olefin may be substituted or unsubstituted. By substituted it is meant that the olefin comprises substituents other than hydrogen. Examples of substituents that may be present in substituted olefins include halogen atoms, alkyl groups, alkoxycarbonyl groups, alkoxy groups, and the like. Typically it is preferred that substituents present in the olefin starting material be inert under the hydrosilation reaction conditions. The olefinic compound may also contain an oxirane. Oxirane-containing olefins are valuable raw materials for the synthesis of oxirane-containing organosilicon compounds. The oxirane-containing olefin can generally be any type of an organic oxirane compound having one or more carbon-carbon double bonds anywhere in the molecule. Examples of suitable oxirane-containing olefins include, but are not limited to, allyl glycidyl ether, methallyl glycidyl ether, 1-methyl-4-isopropenyl cyclohexene oxide, 2,6-dimethyl-2,3-epoxy-7-octene, 1,4-dimethyl-4-vinylcyclohexene oxide, 4-vinylcyclohexene oxide, vinylnorbornene monoxide, dicyclopentadiene monoxide, 1,2-epoxy-6-heptene, and 1,2-epoxy-3-butene, and the like.
The amount of olefin necessary to carry out the hydrosilation reaction is generally such that the reaction mixture comprises at least one reactive double bond per Sixe2x80x94H group. The term xe2x80x9creactive double bondxe2x80x9d is defined herein as a double bond that undergoes hydrosilation reaction with Sixe2x80x94H groups under the conditions of the present invention. Examples of reactive double bonds include the vinyl group of 4-vinyl cyclohexene oxide and the aliphatic double bond present in eugenol.
In a particular embodiment of preparing the organosilicon composition, the optional solvent, the olefin, and the platinum catalyst are mixed together prior to addition of the silicon hydride. The method described above is particularly useful for preparing an oxirane-containing organosilicon composition.
In another embodiment, the method of the present invention may be used to prepare an oxirane-containing organosilicon composition having a total weight after a final evaporation step, referred to here as Step (E), in which volatile components of the reaction mixture are removed after completion of the hydrosilation reaction. Such an embodiment comprises: (A) preparing a mixture by combining: i) at least one olefinic compound containing at least one oxirane ring, ii) optionally at least one solvent, iii) at least one hydrosilation catalyst comprising a platinum (II) complex having the formula PtL2X2, wherein each xe2x80x9cLxe2x80x9d is independently selected from the group consisting of ER3, E(OR)3, and E(NR2)3; each xe2x80x9cExe2x80x9d is independently selected from the group consisting of phosphorus, arsenic, and antimony; each R is independently a hydrocarbyl group; and each xe2x80x9cXxe2x80x9d is independently selected from the group consisting of chloride, bromide, and iodide; said hydrosilation catalyst being present in an amount corresponding to an amount of platinum, said amount of hydrosilation catalyst being such that the amount of platinum present in said mixture is in a range between about 1 part and less than 1000 parts per billion relative to the total weight of the oxirane-containing organosilicon composition after the evaporation step (E); (B) heating the mixture formed in step (A) to a temperature from about 50xc2x0 C. to about 250xc2x0 C. in the presence of oxygen, (C) adding to the heated mixture at least one silicon hydride; (D) heating the mixture formed in steps (A)-(C) to a temperature between about 50xc2x0 C. and about 300xc2x0 C. until essentially all of the hydride groups have reacted; (E) an evaporation step comprising heating the mixture formed in steps (A)-(D) under reduced pressure to remove essentially all volatile material to furnish a oxirane-containing organosilicon composition, said oxirane-containing organosilicon composition comprising at least one oxirane ring; and wherein during steps (A)-(E), the oxirane rings either originally present in the olefinic compound or in the oxirane-containing organosilicon composition remain substantially intact. The phrase, xe2x80x9cessentially all of the hydride groups have reactedxe2x80x9d is meant to indicate complete consumption of all silicon hydride groups as determined by an analytical method. An example of an analytical method for this purpose is infrared spectroscopy.
The progress of the hydrosilation reaction may be followed by infrared spectroscopy by monitoring the disappearance of the Sixe2x80x94H absorption (which occurs at about 2100 cmxe2x88x921) of the silicon hydride. When the hydrosilation reaction is judged to be essentially complete, the volatile components, including the at least one solvent, if used, and any excess of the at least one olefin are evaporated under vacuum to afford the desired organosilicon composition. Typically, the product organosilicon compositions prepared by the method of the present invention are essentially colorless materials.
In a particular embodiment, a method for preparing an oxirane-containing organosilicon composition having a total weight after an evaporation step (E) comprises the steps of: (A) preparing in the presence of oxygen a mixture by combining: i) at least one solvent selected from the group consisting of toluene, xylenes, mesitylene and mixtures thereof, ii) 4-vinylcyclohexene oxide, the 4-vinylcyclohexene oxide being present in the mixture in an amount corresponding to a number of moles of 4-vinylcyclohexene oxide; and iii) a hydrosilation catalyst comprising the formula, (PPh3)2PtX2, wherein each xe2x80x9cXxe2x80x9d is independently selected from the group consisting of chloride, bromide, and iodide, where the hydrosilation catalyst is present in an amount corresponding to an amount of platinum, where the amount of hydrosilation catalyst is such that the amount of platinum present in said mixture is in a range between about 1 part and less than 1000 parts per billion relative to the total weight of the oxirane-containing organosilicon composition after the evaporation step (E); (B) heating the mixture formed in step (A) to a temperature from about 110xc2x0 C. to about 150xc2x0 C.; (C) adding to the mixture formed in steps (A)-(B) at least one silicon hydride, where the silicon compound(s) is(are) added in an amount corresponding to between about 0.1 mole and about 1 mole of total Sixe2x80x94H group per mole of said 4-vinylcyclohexene oxide present in the mixture; (D) heating the mixture formed in steps (A)-(C) to a temperature between about 50xc2x0 C. and about 300xc2x0 C. until essentially all of the hydride groups have reacted; and (E) an evaporation step comprising heating the mixture formed in steps (A)-(D) under reduced pressure to remove essentially all volatile material to furnish an oxirane-containing organosilicon composition, wherein the oxirane-containing organosilicon composition comprising at least one oxirane ring; and wherein during steps (A)-(E), the oxirane rings originally present in the 4-vinylcyclohexene oxide and in the oxirane-containing organosilicon composition remain substantially intact.
In yet another embodiment, the method of the present invention provides a curable composition prepared using the general procedure described above, where the composition has a weight, and where the composition comprises less than 1000 parts per billion of platinum relative to the weight of the curable composition.
In the shorthand notation of depicting organosilicon polymer structure: 
The high selectivity of the hydrosilation reaction is utilized to prepare a variety of oxirane-containing organosilicon compositions, such as those represented by formulas (I) to (VI), as shown below, in high purity. These compositions are readily prepared from the corresponding silicon hydride compounds and vinylcyclohexene oxide (hereinafter sometimes referred to as xe2x80x9cVCHOxe2x80x9d) as starting materials. The oxirane-containing organosilicon compositions are valuable monomers for preparing cured epoxy resins, which in turn are particularly valuable for preparing encapsulents for LED""s. 
Using known hydrosilation conditions it is often difficult to prepare high quality, water-white materials. The primary issue is that the reaction must be very selective, afford a very high yield of the hydrosilylated product, and use such low levels of the hydrosilation catalyst that the catalyst can be left in the final organosilicon composition without affecting the shelf life of the organosilicon composition. The reason for this is that the product compositions have high boiling points and high viscosities, making it difficult or impossible to purify them. If such a reaction would avoid a purification step, some silicon compounds would become available in a high level of purity not possible by any other currently known method, as well as dramatically lowering the overall cost of the process. The process cost is lowered by use of much less of the expensive platinum-containing catalyst and elimination of a process for product purification. VCHO is a fairly reactive olefin substrate, readily hydrosilylated by various silicon compounds containing hydride groups. 1,1,3,3-Tetramethyldisiloxane (MHMH) is both reactive and volatile, thus making the preparation of (I) straightforward. Since many other high molecular weight polyfunctional oxirane-containing organosilicon compounds, such as the oxirane-containing organosiloxanes are non-volatile, viscous, and reactive liquids, their purification is practically limited to removal of volatile impurities by vacuum stripping. This results in oxirane-containing organosilicon compositions containing the platinum catalyst residue. Since the starting materials for the hydrosilation reaction are themselves relatively easily purified, one may obtain high quality oxirane-containing organosiloxanes if the hydrosilation is free of side reactions (vide infra) and essentially quantitative conversion is obtained.
The above method can be used for preparing a wide range of oxirane-containing organosilicon compounds, wherein a variety of silanes and siloxanes can be reacted with a variety of oxirane-containing olefins. Furthermore, the hydrosilafion reaction proceeds such that the oxirane rings in the oxirane-containing olefin and in the oxirane-containing organosilicon composition remain substantially intact throughout the course of the reaction and subsequent isolation of crude product. The method avoids the use of tertiary amine stabilizers to prevent the oxirane ring opening. The products are generally obtained as colorless materials, have good shelf life, and show no signs of viscosity increase, indicating that the oxirane ring in the product has not been polymerized.
In one embodiment, the compositions prepared using the methods disclosed herein are used in the manufacture of LED devices. In another embodiment, the present disclosure relates to the LED devices themselves which may be prepared using conventional LED manufacturing techniques which substitute the organosilicon compositions prepared according to the method of the present invention for conventional thermosetting materials. The compositions prepared according to the method of the present invention may be cured using conventional curing techniques to produce a cured composition. These curable compositions are valuable materials for preparing LED devices, and more particularly, the high luminosity LED devices. The curable compositions are used for producing new epoxy encapsulent materials having greater resistance to thermal aging while retaining the desirable properties of existing epoxy materials, such as resistance to crack propagation, ease of handling, high glass transition temperature, good adhesion, and low coefficient of thermal expansion.